A chiral low-molecular-weight amphiphile, L- 18Ala11PyPF(6), was synthesized from L-alanine. Hollow silica nanoworms with circular pore channels parallel to the shell surfaces and holes at the terminals were prepared using the self-assemblies of it as templates via a single-templating approach. The formation of this hierarchical structure was studied by taking TEM images after different reaction time and changing reaction conditions. It was found that the morphologies of the amphiphile-silica assemblies changed gradually during the sol-gel transcription process.